Alkylation of isoparaffinic hydrocarbons



Patented Nov. 4,

' 2,480,181 ALKYLATIOliOI ISOPARAFFINIC 1 2,430,131- FFlCE HYD OOARBONS Carl B. Linn, Chicago, 111., -asoignor to Universal 1 Oil Products Company, Chicago, 111., a corporation of Delaware No Drawing. Application December 29,1941, Serial No. 424,783

' 22 Claims. (01. zoo-sass) This invention relates to a .process involving the treatment of iscparafllnic hydrocarbons, both gaseous and liquid, to produce therefrom branched chain parafilnic hydrocarbons of higher molecular weight. In a more speciflcsense this i 2 portion by weight of liquid hydrogen fluoride invention is concerned with a novel process for alkylating isoparaiflnic hydrocarbons, comprising isobutane and relatively low-boiling normally liquid isoparaffins with gaseous or liquid olefins to produce normally liquid saturated hydrocarbons which may be utilized as components of gasoline suitable for use in airplane and automobile engines.

These isoparaflinic and oleflnic hydrocarbons have been utilized in alkylation reactionsin the presence of hydrogen fluoride alone or of hydrogen fluoride diluted with relatively small quantities of water. The present type of catalyst is a marked improvement-over previous catalysts containing hydrogen fluoride in that the activity of the catalytic material may be controlled more accurately by proper dilution with non-aqueous substances which are relatively inert catalytically but which have substantial solubilities in liquid hydrogen fluoride.

In one specific embodiment the present invention comprises the alkylation of isoparafllnic hydrocarbons with olefinic hydrocarbons in the presence of a catalyst comprising essentially a major proportion of hydrogen fluoride and a relatively minor proportion. of an inorganic compound soluble therein.

A feature of the present invention is the dilution of substantially anhydrous hydrogen flu.- oride with a non-aqueous diluent so that the ordifluoride on catalytic condensation reactions among hydrocarbons is moderated to the extent that reactions of alkylation occur in preference to other less desirable reactions. Alkylation is essentially a complex reaction since the simple union of paraflinic and oleflnic molecules to give the so-called primary reaction product is accompanied by many side reactions, among which are decomposition or cracking reactions and isomerization, which can, under certain conditions, change a substantial proportion of the primary product such as iso-octanes into a mixture quality of the hydrocarbon and a'relatively minor proportion by weight of an inorganic salt soluble therein, said inorganic salt comprising particularly the fluorides and the sulfates of the alkali metals. The term isoparaffin is herein used broadly to include all alkylatable branched chain paramns. The reaction of the present process is effected under controlled conditions of temperature and pressure until the olefins have been substantially consumed and a substantially saturated hydrocarbon product is formed which boils within the boiling range of asoline.

Isobutane is the isoparamn commonly subjected to alkylation although higher molecular weight isoparaflins may also be-reacted with oleflns un-v I der similar or modified conditions of operations to produce branched chain parafllns of higher boiling point than the isoparaflins charged to the process. However, as the higher molecular weight isoparaflins such as iscpentane, isohexane, etc.,

are themselves valuable constituents of gasoline,

, they are consequently used less commonly as 35. narily vigorous reaction of anhydrous hydrogen charging stocks for the alkylation process than is isobutane. Mono-olefins, and particularly those containing from 3 to about 16 carbon atoms per molecule, are utilizable for alkylating isoparafllns in the presence of a mixture of hydrogen fluoride and a diluent or spacing agent as herein described, although the common olefin-containing charging stocks are often limited to hydrocarbon fractions containing propene and butenes and certain amounts of ethylene. Normal parafflns frequently present in hydrocarbon fractions. containing propene and butenes dilute the reacting hydrocarbons but are separable from the alkylation products by distillation.

the alkylation product, while an isoparaflin such as isobutane, which is also separated from the reaction product, is recycled to further alkylation treatment.

In order to favor the alkylation reaction rather than olefin polymerization, the hydrocarbon charging stock including the isoparaflin and added olefin-containing fraction may be commingled with recycled isoparaflln so that the ratio of isoparaflin to olefin in the total hydrocarbon mixture charged to the alkylation zone is approximately 5:1. In some cases this ratio may be as low as about 1:1 or as high as 10:1, or more, the exact ratio being somewhat dependent upon the particular isoparaflin and olefln or olefin-containing mixture charged.

parts by weight of The amount or hydrogen fluoride-containing catalyst employed is. preferably from about lfl to about parts by weight of catalyst per 100 hydrocarbons undergoing treatment at any one time, although in some operations other ratios of catalyst to hydrocarbons may be used. The concentrations of Thus pro- .pane and normal'butane may be removed from hydrogen fluoride in the composite catalysts which I have found desirable are limited by the solubilities in liquid hydrogen fluoride of the salts chosen as catalyst diluents or spacing agents. Depending upon the reactivity of the hydrocarbon components in a given allrylation reaction, hydrogen fluoride of different concentratlons and different proportions of hydrogen fluoride and diluents may be employed to form active alkylating catalysts.

Alkylation reaction temperatures between about and about 50 C. are preferred, although satisfactory results may be obtained at temperatures as low as about 30 and as high as about +100 .0. when reacting isoparamns with oleflns in the presence of a mixture of hyis determined by olubility relations, the moderatdrogen fluoride and an inorganic spacingagent proportions of hydrogen fluoride and diluent may be varied to produce good results provided they are co-ordinated properly with the reaction temperature and rate of charge of the isoparaifln and olefin hydrocarbons. For instance, the reactionlof isobutane with propene may require more severe conditions such as a somewhat higher temperature, ,a longer'time of contact, or a catalyst containing a higher proportion of hydrogen fluoride to diluent than that used for catalyzing the reaction of isobutane with the more reactive isobutene. Superatmospheriic pressure, generally not in excess of about atmospheres, is employed to assist the reaction and to prevent undue loss of the reactants and catalyst by vaporization and, when desirable, to maintain the hydrocarbons and catalyst in substantially liquid state or to effect liqueflcation of a portion of the reaction mixture.

As spacing agents or diluents forliquid hy-' drogen fluoride to produce alkylation catalyst composites suitable for use in the reaction'of isoparafiins with olefins, the present invention contemplates the use of a number of inorganic compounds which are soluble to a substantial extent .in liquidhydrogen fluoride. Suitable inorganic diluents include such compounds as the fluorides and sulfates of the alkali metals and particularly the fluorides and sulfates of sodium and potassium, including acid salts and normal salts. Under certain conditions the hydrogen fluoride and normal salts which may be added thereto may produce in the alleviation reaction vmixture double salts or acid saltsjof which potassium acid fluoride, KHFz, and sodium acid fluoride, NaHFa, are representative. these materials also possessing substantial solubilities in liquid hydrogen fluoride.

From the statements hereinabove set forth concerning the types of inorganic salts which may be employed as diluting or spacing materials for hydrogen fluoride, it will be evident that a large number of catalyst composites of varying compositions may be made according to the needs of diflerent alkylation reactions. However, the different diluents or spacing agents are not necessarily equivalent in their action.

' While in most cases the activity of the alkylating composite employed is due principally to the hydrogen fluoride, it is recognized that the inorganic compounds added thereto may'at times exert a definite chemical; influence upon the reactions other than merely moderating the eflect of the hydrogen fluoride. It is also evident that the selection of any particular alkali metal salt log effect of said alkali metal salt on the activity of this catalyst utilized in the alkylation of the isoparafllnic hydrocarbons involved, the general operating conditions, and the matter of economy in the cost of the reagents.

The process of the present invention is carried out in either batch orcontinuoustypes of operation. In a simple batch type process, an isoparaflln'to be alkylated such as isobutane, is brought to the alkylating temperature within the approximate range specified andin the presence of the necessary amount of catalyst mixture comprising liquidhydrosen fluoride and a salt of an alkali metal employed as a spacing ent, and alkylation is effected by the gradual introduction of an olefin, or preferably of an olefin-iscparaflln mixture, under the surface .of the liquid catalyst which is stirred mechanically to effect intimate contact between the catalyst'and the reacting hydrocarbons and to delay the setting-out andseparation of the catalyst which is heavier than the liquid hydrocarbon mixture. Alkylation may be allowed to progress to different stages of reaction. In the case of the alkylation of isobutane by propene or butenes, good products from the standpoint of high antiknock gasoline are produced usually by maintaining at all times in the reaction zone a molar excess of isoparaflin to olefin. The presence of such an excess of isoparafiins, generally at least 2 molecular proportions of isoparafilns per molecular proportion of olefin, tends to minimize undesirable polymerization reactions.

The mixture of alkylation products and catalyst composite is removed periodically from the batch type process and separated into a hydrocarbon layer and a catalyst layer, the latter being sequent alkylation treatment in the alkylation zone of the process.

It is usually preferable to carry out the alkylation reaction on a continuous basis by withdrawing from the alkylation reactor a complex mixture of excess unreacted isoparamns and admixed normal paramns, an alkylate of gasoline boiling range, higher boiling hydrocarbons, and catalyst composite, said complex mixture being withdrawn at substantially the same rate as thatat which the fresh hydrocarbon charging stock and catalyst are supplied to the alkylation reactor. In order to keep low the competing olefin polymerization reaction, the molar ratio of isopraamns to oleflns in the alkylating zone is kept relatively high throughout the entire reaction. The ratio of isoparailln to olefin is subject to some variation and is affected considerably by the method of introducing the olefin-containing fraction and by the efficiency of mixing. As the process is usually operated, sufllcient pressure is maintained upon the reaction mixture to keep a substantial proportion thereof in liquid state. The exact pressure necessary depends both upon the composition of the reaction mixture and the temperature employed. The alkylation reactor used in the process consists quite often of a coil or tower provided with baflles, oriflce plates, or other mixing devices, or 'a vessel provided with a stirrer or other mechanical means of agitation although any method may be employed that satisfactorily 01f mixture of salts for use with hydrogen fl or de W effects intimate contact of the reacting hydrocarbone and mixture of catalyts and spacing agent employed.

The following example is given to indicate results obtainable by the use of the present process, although it is not intended to limit the scope of the invention in exact correspondence with the example.

A mixture of 360 parts by weight of commercial liquid hydrogen fluoride (containing 98% by weight of hydrogen fluoride and 2% water) and 40 parts by weight of potassium fluoride is charged to a steel autoclave of approximately 5000 volumes capacity equippedwith a pressuresealed stirring device. The autoclave is maintained at approximately 38 C. by immersion in a cooling bath of appropriate temperature and 3000 volumes of a liquid mixture, consisting of isobutane and normal butene in the ratio of 3 molecular proportions of isobutane and 1 molecular proportion of normal butene, is introduced continuously to the autoclave over a period of two hours while the reaction mixture in the autoclave is stirred mechanically. After completing the addition to the autoclave of the mixture of isobutane and normal butene, the stirring is stopped, the hydrocarbon layer is separated from the hydrogen fluoride-containing catalyst layer, the latter being returned to further use in another run. The hydrocarbon layer is debutanized, washed with water and caustic'soda solution to remove dissolved hydrogen fluoride, dried, and distilled to separate therefrom a substantially saturated fraction of gasoline boiling range containing a relatively high proportion of branched chain octanes. The isobutane recovered in the debutanization of the alkylation product is returned to further contact with normal butenes and a mixture of fresh and used catalyst to produce a further quantity of alkylation product.

From 3000 volumes (approximately 1700 parts by weight) of the isobutane-normal butene mixture treated there is obtained approximately 850 parts by weight of water-white, normally liquid, saturated hydrocarbons containing less than 0.001% by weight of organically combined fluorine and having an end-boiling point of 450 F. The resulting normally liquid hydrocarbons are equivalent to approximately 200% by weight of the butenes charged to the process. 90% of the liquid hydrocarbon products boil below 300 F. and are thus in the boiling range of aviation gasoline. The aviation gasoline fraction has an octane number of 93.

Although the salts of alkali metals herein set forth are preferred as materials to be added to liquid hydrogen fluoride to modify its alkylating activity in accordance with the present invention,

other inorganic compounds and particularly fluorides and oxyfluorides havin normal boiling points below about 300 C. may also be comminto indicate the character of the process of the present invention and the nature of results obtainable, although neither section is introduced with the idea of unduly limiting the generally broad scope of the invention.

I claim as my invention: 1. An alkylation process which comprises re- 6 acting an isoparafiln with an olefln in the presence of a liquid hydrogen fluoride catalyst having dissolved therein a minor proportion of an inorganic salt soluble in liquid hydrogen fluoride and selected from the group consisting of the alkali metal fluorides and sulfates.

2. An alkylation process which comprises reactingan isoparafl'ln with an olefln in the presence of a liquid hydrogen fluoride catalyst having dissolved therein a minor proportion of an alkali metal fluoride.

3. An alkylation process which comprises reacting an isoparaflin with an olefln in the presence of a liquid hydrogen fluoride catalyst having dissolved therein a minor proportion of an alkali metal sulfate.

4. A process for producing gasoline which comprises contacting an isoparafllnic hydrocarbon with an oleflnic hydrocarbon under alkylating conditions in the presence of a catalystcomprising essentially a major proportion by weight of liquid hydrogen fluoride and a relatively minor proportion by weight of an inorganic salt s'oluble therein and selected from the group consisting of the alkali metal fluorides and sulfates, whereby the isoparaflin is alkylated and a substantially saturated hydrocarbon product is formed which boils within the boiling range of gasoline.

5. Aeprocess for producing gasoline which comprises contacting an isoparaflinic hydrocarbon with an oleflnic hydrocarbon under alkylating conditions in the presence of a catalyst comprising essentially a major proportion by weight of liquid hydrogen fluoride and a relatively minor proportion by weight of an alkali metal fluoride soluble therein whereby the isoparaflin is alkylated and a substantially saturated hydrocarbon product is formed which boils within the boiling range of gasoline.

6. A process for producing gasoline which comprises contacting an isoparaflinic hydrocarbon with an oleflnic hydrocarbon under alkylating conditions in the presence of a catalyst comprising essentially a, major proportion by weight of r liquid hydrogen fluoride and a relatively minor proportion by weight of an alkali metal sulfate soluble therein whereby the isoparaflin is alkylated and a substantially saturated hydrocarbon product is formed which boils within the boiling range of gasoline. I

7. A process for producing gasoline which comprises contacting. an isoparaifinic hydrocarbon with an oleflnic hydrocarbon at a temperature of from about 30 to about +100 C. in the presgled with liquid hydrogen fluoride to form comence of a catalyst comprising essentially a major proportion by weight of liquid hydrogen fluoride and a relatively minor proportion by weight of an inorganic salt soluble therein and selected from the group consisting of the alkali metal fluorides and sulfates, whereby the isoparaflin is alkylated and a substantially saturated hydrocarbon product is formed which boils within the boiling range of gasoline.

8. A process for producing gasoline which comprises contacting an isoparafflnic hydrocarbon with an oleflnic hydrocarbon at a temperature of from about 30 to about C. in the presence of a catalyst comprising essentially a major proportion by weight of liquid hydrogen fluoride and a relatively minor proportion by weight of an inorganic salt soluble therein and selected from the group consisting of the alkali metal fluorides and sulfates, and under a pressure suiflcient to maintain the reacting hydrocarbons and catalyst in substantially liquid state whereby the 7 7 isoparaflinic hydrocarbon is alkylated and a substantially saturated hydrocarbon product is boilswithin the boiling range oi boiling olefin at a temperature of from about -30 to about +100 C. in the presence of a catalyst comprising essentially a major proportion by weight of liquid hydrogenfluorideand a relatively minor proportion by weight of an inorganic I salt soluble therein and selected from the group consisting of the alkali metal fluorides and sulfates, and under a pressure sufllcient to maintain the reacting hydrocarbons and catalyst in substantially liquid state whereby the isobutane is alkylated and a substantially saturated hydrocarbon product is formed which boils within the boiling range of gasoline.

10. 'The process of claim 9 further characterized in that the relatively low-boiling olefin comprises propene.

11. The process of claim 9 further characterized in that therelatively low-boiling olefln comprises a butene.

12. The process of claim 6 further charactermetal sulfate comprises a proportion of hydrogen fluoride and a relatively minor proportion of an inorganic salt selected from the group consisting of the' alkali metal fluorides and sulfates at a temperature of from about --30 to about +100 C. and under a pressure sufilcient to maintain in liquid state a substantial proportion of the reacting hydrocarbons and catalyst whereby the isobutane is alkylated and a substantially saturated'hydrocarbon product is formed containing a relatively high proportion of iso-octanes.

7 comprises contacting at least 1 molecular propor- I 15. A process for producing gasoline which comprises contacting at least 1 molecular proportion of an isoparafiinic hydrocarbon with 1 molecular proportion of an oleflnic hydrocarbon under alkylating conditions in the presence of a catalyst comprising-essentially a major proportion by weight or liquid hydrogen fluoride and a relatively minor proportion by weight of an inorganic salt soluble therein and selected from the group consisting of the alkali metal fluorides and sulfates, whereby the isoparaflin is alkylated and a substantially saturated hydrocarbon product is formed which boils within the boiling range of gasoline.

formed which 17. A process for producing gasoline which comprises contacting at least 1 molecular proportion of an isoparafllnic hydrocarbonwith 1 molecular proportion of an oleflnic hydrocarbon containing at least 3 carbon atoms per molecule at a temperature of from about -30 to about +100 0. in the presence of a catalyst comprising essentially a maiorproportion by weight of liquid hydrogen fluoride and a relatively minor roportion by weight of an alkali metal fluoride soluble .therein and under a pressure sufllcient to maintain in liquid state substantial proportions of the reacting hydrocarbons and catalyst whereby the isoparaflinic hydrocarbon is alkylated and a substantially saturated-- hydrocarbon product is boils within the boiling range of gasoline.

18. .A process for producing iso-octanes which comprises contacting at least 1 molecular proportion of isobutane with 1 molecular proportion of abutene at a temperature of from about 30 to about +100 .C. in the presence of a catalyst comprisin essentially a relatively major proportion by weight of liquid hydrogen fluoride and a relatively minor proportion by weight of an alkali metal fluoride soluble therein, whereby the isobutane is alkylated and a substantially saturated hydrocarbon product is formed containing sub- 'stantial proportions of iso-octanes.

19. A process for producing iso-octanes which tion of isobutane with 1 molecular proportion of a butene at a temperature of from about -30 to about +100 C. in the presence of a. catalyst comprising essentially a relatively major proportion by'weight of liquid hydrogen fluoride and a relatively minor proportion by weight of an alkali metal fluoride soluble therein and under a pressure suflicient to maintain the reacting hydrocarbons and catalyst in substantially liquid state whereby the isobutane is alkylated and a substantially saturated hydrocarbon product is formed containing substantial proportions of isooctanes.

20. A method for catalytically reacting an olefin hydrocarbon with an-isoparaflin hydrocarbon which comprises contacting such reactants with each other under alkylating conditions of temperature and pressure in the presence of catalytic material comprising a major proportion of hydrogen fluoride and a minor proportion of a double fluoride of hydrogen and an alkali metal 21. In the alkylation of an isoparaflin with an olefin, the improvement which comprises,v reacting said isoparaflin and olefin in the presence of a catalyst comprising a major proportion of hydrogen fluoride and a minor proportion of an alkali metal acid fluoride.

22. In the alkylation of an isoparaflin with an olefin, the improvement which comprises reacting said isoparaflin and olefln in the presence of catalytic material resulting from the commingling of an alkali metal fluoride with a greater amount of hydrogen fluoride.

CARL B. LINN.

REFERENCES CITED.

The following references are of record in the file of this patent:

UNITED STATES PATENTS Number v Name Date 2,285,785 Seguy June 9, 1942 2,214,481 Schmerling et a1. Sept. 10, 1940 

